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United States Patent The present invention relates to bis-triazinylaminostilbene compounds; more particularly it concerns bistriazinylamino-stilbene compounds of the general formula 3,177,20? Patented Apr. 6, 1965 "ice pared by various methods, for instance in the following manner: in the first stage at 0l0 C. 2 mols of cyanuric chloride are condensed with 1 mol of 4,4-diaminostilbene- 2,2-disulfonic acid, in the second stage at 10-40 C. the next two chlorine atoms are replaced by the radicals of suitable aromatic amines and thereupon in the third stage at 70-98 C. one of the two chlorine atoms still present in the triazine rings is likewise replaced by the radical of a suitable aromatic amine, whereas the other chlorine atom is replaced by the NH -group or by the radical of an aliphatic or araliphatic amine.

Especially suitable optical bleaching agents are the bistriazinylamino-stilbene compounds of the abovementioned general formula, wherein X X and X stand for wherein X X and X stand for the radicals of aromatic amines, and X, for NH or for the radical of an aliphatic or araliphatic amine, whereas Y represents hydrogen or an inorganic or organic cation such as sodium, potassium, calcium, NH or an aliphatic amine. The amine radicals may be substituted, for instance by alkyl groups, fluorine or chlorine, hydroxyl or alkoxy groups, sulfone groups and acid groups or groups derived therefrom, e.g., carboxylic, nitrile, sulfonic and sulfonamide groups.

The bis-triazinylamino-stilbene compounds of the present invention which in general show a bluish fluorescence in daylight can be used as optical bleaching agents in a manner known per se; they go surprisingly well on materials made of cellulose fibres as well as on materials made of polyamide fibres from neutral and alkaline treating baths. Washing agents which contain such optical bleaching agents can therefore be used for textile materials of polyamide fibres, even if the washing agents-show an alkaline reaction. By adapting the washing method in the usual manner to the kind of the fibres of the textile materials, a whitening effect is obtained which in both cases is highly satisfactory. Such a result could not be obtained by using the optical bleaching agents hitherto known.

The compounds of the present invention can be prethe radical NH.C H and X for NH; or the radical of an aliphatic or araliphatic amine, for instance for one of the following radicals:

Other suitable optical bleaching agents of the abovementioned general formula are indicated in the following table:

TABLE -NH NH-onr,

i Cl

urn-Q0 CH3 NHCHa i Nn-on,-o-oHa H l SOs a 3 011,011,011

TABLE-Continued The quantity of the optical bleaching agents required Z were added to the reaction mixture and the hydrochloric can readily be determined by preliminary tests. acid formed was likewise neutralized with sodium car- The following examples serve .to further illustrate the bonate solution until the pH value 7 wasreached. This present invention without, however, limiting thescope second condensation stagewas completed by slowly heatthereof; the parts given are by weight. ing the reaction mixture to 35 C. while keeping the pH lue at 7. For carr 'n out the third condensation l 1 Va .Ag Efmmp e V stage, 32.1 parts of methyl amine .m the form' of an A Washmg Powder Winch contalns about 50 Percent by about 30 percent aqueous solution and 332 parts of ani- Weight of Y S051p and the usual mponents such line were addedto the reaction mixture and the mixture as Pl m g P ph sfldlllm carbonale and Was boiled under reflux for 2 hours, whereupon the aceal ah s 1S m1Xed Willi Percent y Welghi of tone was distilled 01f andthe remaining solution stirred the Optical bleachlng agent of the formula for 4 hours at 98 C. The pH value of the hot mixture /N\ N i a CaHsHN(7 c-HN-c11=cE--NH-o CNH-CuHs N it. 1 it it SOQNS NaOaS (1 p C NH-CQHE I IH-CHr n a manner known P TeXtfle mafefialsi of Cotton 5 was then adjusted to 5-6 with hydrochloric acid and the or linen are then Washed Wlth the Washms Powder thus mixture was stirred for- 1 hour at to-90 c. The light Obtained in the usual'mannerprefefably at temperatures yellow powdery precipitate Was filtered off-with suction between 80 and 100 C. The textile materials show an hile her, washed with hot water and dried; it was applied excellent brightening efi'ect. as optical bleaching agent in the form of, a mixture with Textile materials of polyamide fibres canbe Washed b ut ;1() 20 f l i d di b t in the usual manner with the same washing powder containing the aforesaid optical bleaching-agent, preferably Example-2 at temperatures up to C. The textile materials thus A washing agent which contains about 30 percent by treated likewise show an excellent optical bleaching effect, a weight of synthetics such as alkyl aryl sulfonates and/or although the washing bath has a pH value or about 10'. 55 fatty alcohol su1fonates,'5 -10 percent'by weight of com:

The optical bleaching agent used was prepared in the plex forming phosphates, -60 percent by weight of following manner: sodium sulfate and 0.3 percent by Weight of the optical 7500 parts of anice-water mixture were mixed at bleachingagent'of the formula N '7 N I sH5HN-(l3 ([3HNCH=CH Nn-c CNH- CaHs N\ S ON Nos i a a a I.

( p V o. ant-cm NH-CaHs i 1 1 V t t w\ GET-CH3 02' C. with a solution of 369 parts of cyanuric chloride is used in the usualv manner for washinglaundry goods in 4400 parts of acetone; to the suspension of the cyanuric of regenerated cellulose orv polyamide fibres. The washchloride obtained there was added at 35 C. the neutral ing bath has'a pH value of about 8.. An excellent whitsolution of 429 parts of thesodium salt of 4,4-d-iarnino- I ening efiiect is obtained on undyed laundry goods, whereas stilbene-2,2'-disulfonic acid in 3500 parts of water. The laundry goods dyed in light pastel shades appear to be mineral acid formed during this first condensation stage more brilliant. 1 was neutralized with sodium carbonate solution ntil the The opticalbleaching agent used waspreparedaccordpH value 7 was reached. After the diamino-stilbene-diing to Example '1 except that in the third condensation sulfonic acid was completelyreacted, 192 parts of ani in stage, besides 332 parts of aniline,"88.-5 parts of mo r-t 5 6 pholine were applied instead of the aqueous solution of and sodium sulfate, and which serves for removing resi- 32.1 parts of methylamine. dues of calcium soaps or the like.

With the same result a washing agent of the above- Laundry goods of cellulose fibres or polyamide fibres mentioned type containing 0.3 percent by weight of the which are rinsed in a bath of about 40 C. containing a optical bleaching agent of the formula 5 agent of the aforementioned type show an essencan be used for washing laundry goods of regenerated tially increased brightnessif compared with laundry goods cellulose or polyamide fibres. 1 i which are treated under equal conditions with a rinsing This optical bleaching agent can be prepared accordagent which does not contain the optical bleaching agent. ing to Example 1 except that in the third condensation The optical bleaching agent used was prepared accordg besides 332 P f aniline, 137 parts of diethanol 'ing to Example 1 except that in the third condensation flmim WW5 pp instead the aqueous 59113003of stage, besides 332mm of aniline, an aqueous solution of methylmneof 133 parts of -6-aminocaproic acid and 55.5 parts of Exam-p 1 3 calcined sodium carbonate in 750 parts of water was applied instead of the aqueous solution of 32.1 parts of A soap base serving for the manufacture of soap flakes madly} e.

is treated in a mixing apparatus, prior to working up in a soap mill, with 0.2 percent by weight of the optical Example 5 bleaching agent of the formula An undyed fabric of polya-mide fibres made from eemulsified in concentrated aqueous soap solution. Launcaprolactam-poly-condensates is immersed at a bath ratio dry goods of cellulose fibres of any kind or of polyamide of 1:30 at room temperature in a neutral bath containing fibres which are washed with the soap flakes in the usual per litre 0.015 g. of the optical bleaching agent of the manner show a whiteness which is remarkably brighter following formula than the same textile goods washed with soap flakes not The bath is heated to C. within 10 minutes and the containing the optical bleaching agent. fabric is kept in the bath for a further 20 minutes with The optical bleaching agent emulsified in concentrated occasional stirring. Thereupon the fabric is rinsed in soap solution can also be added to the suds serving for clear water and finally dried. The polyamide fabric shows the production of curd soap. Laundry goods of celluan excellent optical bleaching eifect.

lose fibres or polyamide fibres which are washed with a 55, In the same manner, a cotton fabric can be optically soap thus obtained show likewise an excellent brightening bleached in the neutral bath described.

efiect. The optical bleaching agent used was prepared accord- The optical bleaching agent used was prepared according to Example 1 except that in the third condensation ing to Example 1 except that in the third condensation stage, besides 332 parts of aniline, 133 parts of 3-(nstage, besides 332 parts of aniline, 88.5 parts of neopentyl- 60 butoxy)-propylamine were applied instead of the aqueous amine were applied instead of the aqueous solution of solution of 32.1 parts of methylamine.

32.1 parts of methylamine.

Example 4 Example 6 3-4 parts of the optical bleaching agent of the formula A washing powder which contains about 50 percent /N\ I /N\ oHt-11No ([JHN@CH=CHNH(\) |C-NH-CHB N 1i 1 N 1i s O3Na N303 s s o 1 111-00115 Nn-omomomonzonr-coom are worked into a rinsing agent which contains complex by weight of ordinary soap and the usual components forming phosphates, sodium silicates, sodium bicarbonate such as complex forming phosphates, sodium carbonate 'of the optical bleaching agent of the formula N I Cl \C// SOgNtl NaOHS in ;a manner known perse. Textile materials of cotton This optical bleaching agent or linen are then washed with the washing powder thus obtained in the usual manner- -preferably at temperatures between 80-100 C. The textile materials show a very 7 good brightening eifect.

Textile materials of. polyamide fibres can be washed in the usual manner with the same washing powder contain temperatures up to 60. C. The textile materials thus treated likewise showva very good-brightening effect, although the washing bath has a pH value of about 10.

' ing the aforesaid optical bleaching agent, preferably at The optical bleaching agent used was prepared in the following manner:

i S OaNa I NH-CaHs 7500 parts of an ice-water mixture were mixed at 0-2" C. with'a 'solutionof 369 parts of cyanuric chloridein 4400 parts of acetone; to the suspension of the cyanuric chloride'obtained there was added at 3-5 C. the neutral.

solution of 429 parts of the sodiumsalt of 4,4-diaminostilbene-2,2'-disulfonic acid in 3500 parts of water. The

mineral acid formed during this first condensation stage wasv I, neutralized with sodium carbonate solution until the pH value 7 was reached. After the diamino-stilbene-disulfonic acid formed was likewise neutralized with sodium carbonate until the pH value 7 was reached. This second condensation stage was completed by slowly heating the reaction mixture to 35 C. while keeping the pH value.

7 acid was completely reacted, 262 parts of m-chloroaniline were added to the reaction mixture and the hydrochloricv ammo? can be used for washing laundry goods of regenerated cellulose, linen or polyamine fibres. 1

. N V N Y V v V N N V 7 l IHCH a p v canbe prepared according to the above prescription except thatin the-second condensationv stage 262 parts of p-chloroanfiline, dissolved in 600 parts of acetone, were applied instead of 262 parts of rn-chloroaniline. V

Example 7 A" washing agent which contains about 30 percent by weight of synthetics such as alkyl aryl sulfonates and/ or fatty alcohol sulfonates, '5-10' percent by weight of complexforming phosphates, 65-60 percent by .weight of sodium sulfate and 0.3 percent by weight of the optical bleaching agent of the formula o'i i I IH-CH3 V V is used in the usual manner for washing laundry goods ofregenerated cellulose or polyamide fibres. The: washing bath has a pH value of about,& A very. good whitening elfect is obtained on undyed laundry goods, whereas laundry goods dyed in light pastel shades appear to be more brilliant.v

The optical bleaching agent used was prepared according to Example 6 except that in the second condensation stage, instead of 262 parts ofm-chloroaniline, a solution of 316 parts of p-amino-benzene-su1fonamideina mixture of 870 parts of acetone and 750 parts of water was applied whereupon the reaction mixture was stirred for a further 2 hours in order to complete this second-condensation stage while maintaining the pH value .at7.

at 7'. For carrying out the third condensation stage, 32.1 Example parts of methyl amine in the form of an about 30 percent 3-4parts of the optical bleaching agent of the formula HNO:S SOs-NH CH V CH nN-o C-HN enacts-Grunt: \CHN (E 2 H2 I [I i H2 N N Y N p OH 7 \C% S OaNa NaOgS \c/ I 7 OH 1 111-0 115 l mit-CH3 aqueous solution and '332 parts of aniline were added to '55 areworked into a rinsing agent which contains complex the reaction mixture and the-mixture was boiled under reflux for 3 hours, whereupon the acetone wasdistilled off and theremaining solution stirred for 1 hour at 98 C. The pH value of the hot mixture was then-adjusted to a 5-6 with hydrochloric acid and the mixture was stirred for 1 hour .at 8090 C. The light yellow powdery precipitate was filtered off with suction while hot, washed forming phosphates, sodium silicates, sodium bicarbonate andsodium sulfate, and which serves for removing residues of calcium soaps or the like. p v

tially increased brightness if compared with laundry goods with hot water and dried;'it was applied as. optical bleach- 7 ing agent in the form of a mixture with about 10-20 percent of calcined sodium carbonate.

With the same result a washing agent of the above-mentioned type containing 0.1 percent by weight of the optical bleaching agent of the formula NaOsS Laundry goods of cellulose fibres or polyamide fibres which are rinsed in a bath of-about 40 .0. containing a rinsing agent of the aforementioned type showan essen- I NH-C sHu sulfoethanolamide in 2600 parts of Water, adjusted to a pH value of 8 with sodium hydroxide solution, was applied, whereupon the reaction mixture was stirred for a further half an hour in order to complete this second condensation stage while maintaining the pH value at 7.

The amounts of optical bleaching agents indicated in l NH-phenyl References Cited in the file of this patent UNITED STATES PATENTS Wendt May 22, 1945 Siegrist May 15, 1956 Ackermann Aug. 5, 1958 FOREIGN PATENTS Italy May 6, 1952 Great Britain Mar. 10, 1954 Canada Aug. 1, 1956 

